Methylenedioxyphenyl compounds containing sulfur as insecticide and pyrethrin synergists



Patented Dec. 11, 195! UNITED STATES PATENT OFFICE METHYLENEDIOXYPHENYL COMPOUNDS CONTAINING SULFUR AS INSECTICIDE AND PYRETHRIN SYNERGISTS Oscar F. Hedenburg, Pittsburgh, PI", aesignor to Harold W. Moburg, trustee, Toledo, Ohio No Drawing. Application September 29, 1948, Serial No. 51,882

in which R is the 3,4-methylenedioxyphenyl radi- I cal or a 3,4-methylenedioxyphenyl-alkyl radical; R1 is a hydrogen atom; R2 is a hydrogen atom, or an alkyl, alkyl carbonyl, alkenyl carbonyl, aryl carbonyl, acyl methyl, or aroyl methyl radical; and R3 is an alkyl, aryl, aralkyl, alkaryl, orallcyclic hydrocarbon radical.

The following examples illustrate in detail the preparation of various compounds falling within the general scope of the present invention. As

the following subject matter indicates, certain of the compounds prepared in the examples were tested in the Peet-Grady test, using the Official Test Insecticide of the National Association of Insecticide and Disinfectant Manufacturers. The Oflicial Test Insecticide contains about 100 mg. of pyrethrins one and two per 100 ml. That insecticide is the standard used in the industry in making comparative tests and is commonly known as the O. T. 1., and shall so'be referred to hereinafter.

Example I 0 all i i i which for convenience will be referred to as No. 198.

The first Feet-Grady tests of this product showed a knockdown of flies which, for some unknown reason, was low but also showed a kill 8 Claims. (01. zoo-ass) that was remarkably high. The synergistic effect,

when compounded with pyrethrins one and two (present in the O. T. I. in quantity of about 100 mg. per 100 cc.) was as follows, according to the initial test:

Ratio kill Composition rm to m down down 2% No. 198, 40 mg. pymthrins Per cent Per cent Per cent 1 and 2 09. 3 66. 3 94 0. T. I 60. 5 39. 7 57 0.4% No. 198, 00 mg. pyrethrim 1 and 2 63. 6 56.4 D 0.5% No. 198, 60 mg. pyrethrim 1 an 69.4 62.2 90 0.3% No. 198, 80 mg. pyrethrim 1 and 2 68.0 59. 7 88 72. 4 47. 2 06 Subsequent repeated tests reveal a normal knockdown and the same high ratio of kill. The results of the second tests were as follows:

Ratio, kill Composition 39.3 Kill to knockdown 7 1% now No. 108, mg. Per cent Per cent Per cent pyrethrlns l and 2 96. 3 94. 7 N OffigNo. 198, mg. pyrethl and 2 96. 8 93. 7 07 s its'aa 'it" 0. mg. p 30 n3; 1 and. 2 98.0 as. 1 as a Do 9a 1 96. 7 98. 5 0. T. I 76.6 76 0.3% No. 198, 40 mg. pymthrins l and 2 09. 2 82. 2 83 O. '1. I 98. 8 01. 7 G). 6

Example II Benzyl mercaptan and isosafrol were heated together for 23 hours at C. to produce the fol- 40 lowing product in a 91% yield:

p-3,4 methylene dioxy phenyl isopropyl benzyl sulfide n E new.

For convenience this compound will be referred to as No. 229, which when tested gave the fol- 66 lowing results.

Ratio kill Knock- Com ltlon Kili to knockpos down down 0.5% No. 229, 64) mg. pyreth- Per cent Per cent Per cent rins I end 2 99.8 93.7 M 0. T. I 29. 8 61. 62

Example H2? Pipemnel was reacted with methyl isoloutyl ketone at low temperature and in the presence of sodium hydroxide, to yield by condensation the compound Piperonnl Methyl isobutyl ketone iiflmethylenedios g at ryl isobutyl ketone (piperonsl met yl uobutyl ketone) iiiio 1k This compound was thereafter reacted with henzyl memapton by heating them together for 2Q hours at 135 C. to produce in about a 99% yield the compound whensyl thio 8-3.4-meth lene dioxy phenyl ethyl isobuty ketone For convenience this compound will be referred to as No. 24%, and when tested gave the iollowing results.

Knoetb Ratio, kill Composition Kill to knockdown down 0.5% No. 244, 50 mg. pyreth- Pa? cent Per cent Per cent rins l and 2 95. 5 88. i 92 0. T. I 96. 7 63. 2 65 Example IV Piperonal and methyl heptenone were reacted together at low temperature in the presence of sodium hydroxide to yield the compound 3,4-mothylene dloxy styryl isohexenyl ketone H H 0 H H H CH;

This compound was thereafter reacted with benzyl mercaptan by heating them together for 24 hours at 138 C. to produce a compound whammy; *o e=3,4=-methy1ene dioxy phenyl ethyi isohexeny. 2:.

For convenience this compound will he referred to as No. 248, which gave the following results Piperonal and methyl hexyi ketonc were re= acted together in the presence of sodium hy= dioxide at low temperature to yield the compound 3,4-methylene diox at (piperonal me yl itiiti ryl heryl ketone exyl ketone) compound was thereafter heated henzyl meroopten to and 200 C... suo= cessively, to yield a mixture containing the Zol= lowing isomers:

a-henzyl thio B-3,4methylene dioxy phcnyl ethyl hexyi ketone, and fl-benzyl thlo B-SA-metlwlene dioxy phenyl ethyl hexyl ketone ,0 iliiiiiii it titiii For convenience this mixture will be referred to as No. 269, which upon testing gave the follow ing results.

Knocb Ratio, kill Composition Kill to knockdown down 0.3:}, No. 269. 40 mg. pyret Percent Percent Per cent H51 and ..i. 99. 5 97 07 0. 'I. I as 8 61. 7 63 a-benzyl thio 3-3.4-methylene dioxy ae'raaoa Example VI Piperonal was reacted with methyl amyl ketone at low temperature in the presence of sodium hydroxide to produce the compound piperonal methyl amyl ketone.

Piporonal methyl amyl ketone Benzyl mercaptan This compound was then reacted with benzyl mercaptan by heating at 130-220 C. to produce a reaction mixture of'the following isomers:

henyl ethyl n-amyl ketone, and B-benzyl thio fl-3,4-met ylene dioxy phenyl ethyl n-amyl ketone ,O Uiiiiiig ll iinlil ,0- liiiiiii. i i l. l i 1i i For convenience this mixture will be referred to as No. 270, which was tested and gave the following results.

Ratio kill knock- Composition Kill to knockdown down 0.37 No. 270 40 mg. pyreth- Per cent 3 Per cent Per cent 113811111112 99.3 -92.9 93 O. T. I 98.8 61. 7 62 Example V II The intermediate of Example V was reacted with amyl mercaptan to yield a mixture of the following isomers:

a-amyl thio 8-3.4-methglene dioxy phenyl ethyl hexyl ketone, and fi-amyl t io B-3,4-methylene dioxy phenyl ethyl hexyl ketone 6 Example VIII Safrol was reacted with amyl mercaptan by heating the reaction mixture to the boiling point of the mercaptan and allowed the reaction temperature to rise asthe reaction progressed. The mixture began to boil at about -C.. and at the end of the seventh day of heating, the temperature of the reaction mixture was 186 C. The product was a brown oil, consisting essentially or a mixture or the following compounds.

0. iii. 0 ill. H,c t H|C {I A ll! Lu a 0 l li For convenience this mixture will be referred to as No. 2'73, and when tested gave the following results.

Ratio kill knock- Composition Kill to knockdown down 0.5% No. 273, 40 mg. pyreth- Per cent Per cent Per cent rins l and 2 99. 7 93.6 93.8 0. 'l. I 98. 9 64 65 Example IX 3,4 -methylenedioxyphenyl benzyl 'thioethyl phenyl ketone having the structural formula was made by heating together 11 gms. of piperonal acetophenone and 8 gms. of ben zyl mercaptan during 17 hours at C. and 3 hours at 200? C. There was obtained 18.5 gms. of crude product. A petroleum distillate solution containing 500 mg. of that product and 40 mg. ofpyrethrins per 100 ml. gave a kill of 86.6% using house flies. The 0. T. I. gave a 69% kill.

Example X 3,4-methylenedioxypheny1 methylphenyl thioethyl hexyl ketone having the structural formula o- ZH- s00 H, H10

IHII

was made by heating for about 40 hours at 137 C. a mixture of 52 gms. of the intermediate unsaturated ketone of Example V and 24.8 gms.

of parathiocresol. The crude product was dis solved in benzol and shaken with aqueous sodium hydroxide solution which extracted 2.6 gms. of parathiocresol. The benzol was dissolved ofif at reduced pressure, and 74 gms. of product was obtained. A petroleum distillate solution containing 500 mg. of that product and 40 mg. of pyrethrins per 100 ml. gave a 97.3% kill using house flies. The 0. T. I. gave a 69.2% kill.

ammo:

7 Example XI 8,4-methylenedioxyphenylpropyl n butylsulflde having the structural formula was made from 81 gms. of safrol in 66 gms. of n-butyl mercaptan by heating during 10 days at temperatures of 126-167 C. 22.5 gms. of butyl mercaptan was added to the 81 gms. of safrol at the beginning of the reaction. The temperature at that time was 144 C., and it rose in 24 hours to 151 C. Then 14,75 gms. of safrol was added, the temperature then being 133 C., and 'it rose after two days of heating to 153 C. 23.75 gms. of the mercaptan was then added, reducing the temperature to 126-C., but after four days of heating it rose to 140 C. gms. of the mercaptan was added during that time, and during three days more of heating the reaction temperature was within the range 149-167 C. After the completion of the reaction, excess butyl mercap tan was distilled off, and the crude product was steam distilled to remove volatile matter. There was obtained 112.5 gms. of a light colored oil, constituting the product. A petroleum distillate solution of the product containing 300 mg. thereof and 40 mg. of pyrethrins per 100 ml. gave a 72.4% kill using house flies. The O. T. I. gave a 59.8% kill.

Example XII 3,4 methylenedioxyphenyl propyl-n-dodecyl sulfide having the structural formula was made by heating together at 114 C. for 24 hours 22.28-gms. of safrol and 25.25 gms. of

'n-dodecyl mercaptan. The product was steam distilled to remove 7 ml. of safrol and other volatile substances, leaving in the distilling flask 42 gms. of a yellow material, constituting the product. A petroleum distillate solution containing 500 mg. of the product and 40 mg. of pyrethrins per 100 ml. gave a 73.5% kill using house flies. The O. T. I gave a 55.4% kill.

Example XIII 3,4 methylenedioxyphenylpropyl cyclohexyl sulfide having the structural formula /0 CHr-CHZ-OHI-S-CGHH 11,0

isopropyl mercaptan, z-ethylhexyl mercaptan. n-octyl mercaptan, thiophenol, 'phenylethyl mercaptan, o-thiocresol, m-thiocresol, the thioxylenols, cycloamyl mercaptan, cycloheptyl mercaptan. etc.

The unsaturated ketones containing the 3,4-

. methylenedioxyphenyl radical used as intermecycloheptyl ketone, methyl p-methylphenyl kesisting of alkyl, aryl, aralkyl, alkaryLand alicyclic was made by heating at about 164 C. for 22 hours 44.5 'gms. of safrol and 29 gms. of cyclohexyl mercaptan. After steam distillation of the reaction mixture, there remained in the distilling flask 43 gms. of a light brown oil, constituting the product. A petroleum distillate solution containing 300 mg. of the product and 40 mg. of

pyrethrins gave a 61.2% kill using house flies.

The .0. T. I gav'e-a'34.9% kill.

Various changes may be made in the specific teachings of the examples to provide additional products falling within the scope of the present invention. Thus, safrol or isosairol may be reacted with methyl mercaptan, ethy mercaptan,

tone, etc. Such ketones may thereafter be reacted with any of the mercaptans heretofore mentioned in the present specification to provide additional products falling within the scope of this invention.

I claim:

1. The addition products of isosafrol and benzyl mercaptan.

2. The method for the preparation of an insecticide which comprises reacting isosafrol and benzyl mercaptan to form an addition product.

3. The addition products of 3,4-methylenedioxystyryl amyl ketone and benzyl mercaptan.

4. The method for the preparation of an insecticide which comprises reacting 3,4-methylenedioxy styryl amyl ketone and benzyl mercaptan to form an addition product.

5. The addition products of safrol and amyl mercaptan.

6. The method for the preparation of an insecticide which comprises reacting safrol and amyl mercaptan to form an addition product.

7. The compound having the generic formula in which R is a substituent selected from the group consisting of the 3,4-methylenedioxy phenyl radical and the 3,4-methylenedioxyphenyl-alkyl radicals; R2 is a substituent selected from thegroup consisting of the hydrogen atom and alkyl, alkyl carbonyl, alkenyl carbonyl, phenyl carbonyl, alicyclic carbonyl, acyl methyl and aroyl methyl radicals; and R3 is a hydrocarbon substituent selected from the group conradicals. 1

8. The method for the preparation of insecticides which comprises reacting a compound of the formula RsSH, in which R3 is a hydrocarbon substituent selected from the group consisting of alkyl, aryl, aralkyl, alkaryl and alicyclic radicals, with a material selected from the group consisting of safrol, isosafrol and compounds having the generic formula Bill...

in which R is the 3,4-methylenedioxyphenyl 9 10 radical and R2 is a substituent selected from the Number Name Date group consisting of alkyl, alkenyl, aryl, aralkyl. 2,433,491 Synerholm Dec. 30, 1947 alkaryl, and allcyclic radicals. 2,442,555 Synerholm June 1, 1948 QSCAR F. HEDENBURG. 2,452,188 Hedenburg Oct. 26, 1948 5 2,456,316 E'rill Dec. 14, 1948 REFERENCES CITED 2,456,991 Prill Dec. 21, 1948 The following references are of record in the 23571957 wachs Jam 4, 1949 me of patent: 2|52L813 Wachs Sept. 12, UNITED STATES PATENTS 10 OTHER REFERENCES Number Name t Prill et a1. Contrib. Boyce Thompson Institute,

2 430,11 Holmes t aL 1947 vol. 14. No.3 (1946), pages 127 to 131. 136. 

7. THE COMPOUND HAVING THE GENERIC FORMULA 